Anthraqbinone compounds and proc-



Patented Feb. 20, 1940 AN'rnaAoUmo vs COMPOUNDS AND PROC- ass Foa comma 'rnaaswrrn James G. McNally and Joseph B. Dickey, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey NoDrawing. Application September 22. 193i,

Serial No. 165,150

Claims.

This invention relates to anthraqulnone compounds. Mcre particularly it relates to amino substituted anthraquinone compounds which, de-

pending on their structure, are suitable tor the dyeing or coloration of organic derivatives of cellulose, wool, cotton, regenerated cellulose and silk. The invention includes the new anthraquinone compounds, the process for their prepare--v tion, the process of dyeing or coloring therewith and materials made of or containing an organic derivative of cellulose colored with said compounds.

Typical organic derivatives 01' cellulose include the hydrolyzed as well as the unhydrolyzed cellulose organic acid esters, such as cellulose acetate, cellulose iormate, cellulose 'propionate or cellulose butyrate, and the hydrolyzed as well as the unhydrolyzed mixed organic acid esters of cellulose, such as cellulose acetate-propionate, cellulose acetate-butyrate, and the cellulose ethers, such as methyl cellulose, ethyl cellulose orlbenzyl cellulose.

It is an object 01- our invention to provide a new class of anthraquinone compounds.

A further object of our invention is to provide a process for the dyeing or coloration of organic derivatives of cellulose.

A specific object is to provide a process for the dyeing orcoloring of materials made of or containing an organic derivative of cellulose wherein the dye is applied directly from an aqueous suspension.

Another object is to provide material made oi or containing an organic derivative of cellulose colored with the anthraquinone dye compounds of our invention.

A still further object is to provide a suitable process for the manufacture of the anthraquinone compounds of our invention.

The anthraquinone compounds, by means of which the above named objects are accomplished or made possible, are characterized in that they contain in an alpha position a radical selected irom the group consisting of wherein B represents hydrogen, -(CH2)6H or group consisting of (CH2) :NHI, wherein :1: represents a whole hum ber above zero, and n is a whole number above zero. advantageously, n and m are small whole positive numbers not greaterthan 4. Again, ad vantageously B is ahydrogen atom.

While our invention relatesto anthraquinone compounds characterized in the manner just described, we have found that anthraquinonc compounds having the general formula:

wherein A represents a radical selected from the wherein B represents hydrogen, .-(CH:):0H or t (CH2) :NHa. wherein x represents a whole number above zero, and n. is' a whole number above zero and wherein A; may be the same as A and.

in addition may bea member selected from the; group consisting of ahydroxy group, an amino" group, an alkylamino group, a, hydroxyalkylamino group, an arylamino group, an alkarylaminc, a R

hydroarylaminc group, a heterocyclic amino compoundsoi our invention may be prepared in l a satisfactory andadvantageous way by condens-- ing a leuco anthraquinone with an amine selected from the group consisting of l wherein B and n have the meaning previously assigned to them. These amines, for the sake of simplicity, will be referred to herein as "luran amines as may properly be done. Leuco anthraquinones suitable for use are those containing an alpha. negativesubstituent. capable of being replaced by an amino group by the action of an amine. Negative substituents capable of such replacement include, for example, the hydroxy anthraquinone and leuco l-hydroxy--chloroanthraquinone. 1 hydroxy-4 nitroanthraquinone and l-nitro anthraquinone, for example, may likewise'be condensed with a. "furan amine to form compounds included within thescope of our invention. l V I I Examples of furanamines employed in the process 01' our-invention include 7 nc--cn n CH:NH:

iuriurylamino no-----on V n g-omcmNm p-mryiothylamina and Ec--on H -omomcnmm 1 'rinrylpmpylaniine Hydrogenated derivatives of the above compounds such as H V Bic-41! m I cmNH;

tatrahydroiurmrylaniino and H1C-CH| n H: -OHaOHaNH;

p-tab'ahydroiurylothylamine for example, likewise maybe employed in the the above mentionedrturan amine compounds is given hereinafter. Tetrahydroiuriurylamine may be prepared as described by Winans and Adkins,

Journal American Chemical Society, vol. 55, 2051- (1933) s-Furylethylamine and x' -Furylpropylqamine may-be prepared as described by Takamoto, J. Pharm. ,Soc. Japan, vol. 490, 1084 (1922) and vol. 48, 686 (l928),respectively.

I V The exact method employed for the prepara- 15 tion of the compounds of our inventionis dependent may be present and in such case they maybe the same or difierent. Where two difierent furan amino groups are to be present, the condensation may be carried out with both amines present or stepwise.

Where the desired anthraquinone compound,

is to contain both a. furan amine radical and another substituent, an amine radical, for example, the condensation reaction may similarly be carried out with both amines present, or stepwise. Where this latter procedure is employed, the leuco anthraquinone may first be caused to react with one molecular equivalent weight of a turan' amine and then with the desired amine or the leuco anthraquinone may first be caused to react with one molecular equivalent weight of an amine, other than a iuran amine, and then with the desired furan amine.

Anthraquinone compounds containing substituents in addition to amino substituents may be obtained by treatment of the amino anthraquinone compound by known methods to cause the compound to be substituted with the substituent group desired to be added thereto and in some cases by proper selection of the anthraquinone starting material.

Amines, other than furan amines,-which may be employed include, for example, methylamine, ethylamine, propylamine, butylamine, ethanolamine, propanolamine, butanolamine, aniline o-m-p-phenylene diamine, naphthylamine, o- -mp-toluidine, benzylamine, cyclohexylamine and cyclobutylamine.

The reactions above referred to may be carried out in water or ina solvent diluent medium such as ethanol, butanol, isobutyl alcohol or pyridine, for example. Where a leuco anthraquinone is employed as the starting material, the resulting leuco anthraquinone dye compound may be oxidized to the non-leuco form in any suitable manner. Where pyridine, for example,is the diluent medium employed, the oxidation may be carried out with air. The oxidation may likewise be carried out employing a perborate oxidizing agent, such as sodium perborate, for example. This latter oxidizing agent is of general utility and may be employed in the case of all the diluent mediums above mentioned. v

.The nuclear non-sulfonated compounds of our invention find particular application for the dyeing or coloration oi. organic derivatives oi. cellulose, especially cellulose acetate silk. The nuclear suli'onated compounds possess little or no application for the dyeing or coloration of organic derivatives of cellulosebut may be employed as dyes for textile materials such as cotton, silk, regenerated cellulose and wool. In general, compounds which are sulfonated, but non-nuclearly, likewise find application as dyes for cotton, silk, regenerated cellulose and wool. g

Where the anthraquinone nucleus is substituted with an aryl or hydroaromatic group, these groups may in turn be substituted with an amino group which -,may be treated with alkyl chlorohydrins such as ethylene, propylene, trimethylene or glycerol chlorohydrin to yield an aliphatic hydroxy substituted amino group.

The following examples illustrate the preparation of the compounds of our invention.

Example 1 24 grams of leuco quinizarin are dissolved in 250 cc. of pyridine along with 9.7 grams oi. furfurylamine and the mixture is refluxed for two hours. The leuco compound formed is oxidized with air following which the desired dye compound is obtained by concentrating the pyridine solution. It has the following probable formula:

E "EZ and dyes cellulose acetate silk a violet color from a water suspension.

Example 2 i 24 grams of leuco quinizarin are added to 500 cc. of ethyl alcohol together with 10.1 grams-of tetrahydrofurfuryiamine and the mixture is refluxed for four hours. The leuco compound formed is oxidized by adding sodium perborate to the boiling reaction mixture and the desired dye compound formed by this oxidation is recovered by concentrating the alcoholic mixture. The dye has the following probable formula:

and dyes cellulose acetate silk a violet shade from a water suspension of the dye.

Example 3 and dyes cellulose acetate silk a purple color from a water suspension.

Example 4 24 grams of leuco 1,4-diamino anthraquinone are dissolved in 250 cc. of pyridine, 21.3 grams (10% excess) of furfurylamine are added and the resulting mixture is refluxed for three hours.

The leuco dye c'ompound formed is oxidized with air and the dye compound formed by the oxidation treatment is recovered by concentrating the the following pyridine solution. The dye compound of the example has the following probable formula:

E Kiwi! o Non,- H

. o v and dyes cellulose acetate silk a blue color from its water suspension. H

Example 5 24 grams of leuco quinizarin are placed in 500 cc. of ethyl alcohol together with 22.2 grams (a: excess. over that theoretically required). of

tetrahydrofurfurylamine and the resulting: mireture is refluxed for three hours. The leuco dye compound formed is oxidized with air to give the desired dye compound which is recovered by son centrating the alcoholic solution. The dye compound has the following probable formula:

and dyes cellulose acetate sill: a blue color from a water suspension.

Example 6 23.9 grams of leuco 1-hydroxy-4-aminoanthraquinone are added to 500 cc. of alcohol together with 9.7 grams of furfurylamine and heated at a refluxing temperature until the reaction iscomplete. The leuco dye compound is poured into water and oxidized with sodium perborate, flltered, washed with water and dried. The dye compound has the following probable. formula:

0 NHi no-e-on -CHran and colors cellulose acetate purple shades from an aqueous suspension of the dye. This same compound can be prepared in the manner described above by substituting leuco l-methoxy- 4-aminoanthraquinone for the leuco l-hydroxy- Q-aminoanthraquinone of the example.

Example 7 24 gramsof leuco quinizarin are dissolved in 250 cc. of pyridine together with 6.2 grams of ethanolamine and the resulting mixture is refluxed for three hours. 9.7 grams of furfurylamine are then added and refluxing is continued for an additional three hours. The leuco dye compound formed is then oxidized with air and the desired dye compound formed thereby is recovered by concentratingthe pyridine solution.

The dye-compound has the following formula:

probable HC-CH A g-cm-cmon and dyes cellulose acetate blue shades from a water suspension of the dye.

Example 8' -24 grams of leuco quinizarin are dissolved in .250 cc. of pyridine together with 13.6 grams ,1 1 excess) of sodium taurinate and 11.1 grams (10% excess) w of tetrahydrofurfurylamine. The resulting solution is then refluxed for four hours and theleuc'o dye compound formed is oxidized with air. The desired dye compound may be recovered by concentrating the pyridine solution.-

It has the following probable formula:

N-CHr-C H and dyes cellulose acetate silk a blue color from a water solution of the dye which may contain sodium chloride. I

Example 9 24' grams of leuco quinizarin are added to 400 cc. of ethyl alcohol together with 11.1 grams of tetrahydrofurfurylamine and the mixture resulting' is refluxed for three hours. 3.5 grams of methylamine are then added and refluxing is continued for an additional three hours. The

leuco dye compound formed is workedup as described in Example 6. The dye formed has the following probable formula:

and dyes cellulose acetate blue from a water suspension.

Example 10 24.9 grams of leuco quinizarln are dissolved in 300 cc. of pyridine together with 9.7 grams of furfurylamine and 7.5 grams of HnNCHzCHzCHzOH and the mixture resulting is refluxed for 6 hours. The leuco dye compound formed is oxidized with air, for example, and the desired dye compound therebyformed is recovered by concentrating the pyridine solution. 'Ihe dye has the following probable formula:

0 -cmcmcmon Q1? I Bib-EH s H and dyes cellulose acetate silk a blue shade from an aqueous suspension.

HzNCHzCHOHCHe may be substituted for the HzNCHzCHzCI-IzOH of the above example to obtain a dye compound of the following formula:

H l O N-CHsCHOHCHI which colors cellulose acetate silk blue from an aqueous suspension.

Example 11 3 NEG-NH:

and dyes cellulose acetate silk blue-green shades from a water suspension.

Example 12 10 grams of the dye obtained in Example 11 are refluxed with 15 grams of ethylene chlorohydrin and 5 grams of dry sodium acetate for one or two hours. Part of the chlorohydrin may be recovered by distillation and thedye compound formed by the reaction may be precipitated by pouring into water and recovered by filtration. It has the following probable formula:

and dyes cellulose acetate silk bluish-green shades from an aqueous suspension.

Furfurylamine can be subsituted for tetrahydrofurfurylamine of Example 11 and the dye compound formed can be treated as in Example 12 to obtain the corresponding furfurylamine derivative which likewise dyes cellulose acetate silk bluish-green shades from an aqueous suspension.

Example 13 24 grams of leuco quinizarin, 3.1 grams of methylamine and 400 cc. of ethyl alcohol are charged into an autoclave and heated at 90-l00 C. for three hours with stirring. 10.7 grams (10% excess) of furfurylamine are then added and the heating is continued. When the reaction is completerthe autoclave is opened and the leuco dye compound formed is oxidized by passing air into the hot reaction mixture- The dye compound resulting may be recovered by concentrating the alcoholic mixture. This dye compound has the following probable formula:

and dyes cellulose acetate blue shades from a water suspension.

Example 14 24 grams of leucoquinizarin and 11 grams of benzylamine are refluxedin 300 cc. of pyridine for three hours. 11.1 grams (10% excws) of tetrahydrofurfurylamine are then added and the refluxing is continued for four hours. The leuco dye compound formed is oxidized by treatment with air to form the desired dye compound which may be recovered by concentration of the pyridine solution. The final product of the reaction has the following probable formula:

and dyes cellulose acetate blue shadesfrom an aqueous suspension.

While our invention has been illustrated with reference to various furfurylamino anthraquinone and tetrahydrofurfurylamino anthra accordance with the process of our invention and included within the scope of our invention include: l-furfurylamino 4 benzylamino anthraquinone, l furfurylamino 4 cyclohexylamino anthraquinone, l-tetra-hydrofurfurylamino 4 cyclohexylamino anthraquinone, l-furfurylamino- 4 tetrahydrofurfurylamino anthraquinone, 1 furfurylamino-4-cyclobutylamino anthraiquinone, 1 tetrahydrofurfurylamino anthraquinone, 1 furfurylamino 4 ethylamino anthraquinone, 1- furfurylamino 4 hydroxyethylamino anthra quinone, 1-furfurylamino-l-p-phenylene diamino anthraquinone, and l-furfurylamino--o-tolyl amino ,anthraquinone.

In order that the application of the compounds of our invention may be clearly understood, their application for the direct dyeing or coloration of materials made of or containing an organic derivative of cellulose, and more particularly cellulose acetate silk, is described hereinafter. Although the remarks are more particularly directed. tothe dyeing or coloring of the above mentioned materials, those pertaining to temperature, the dispersing agents and the amounts of dispersing agent and dye which may be employed, for example, are, of general applicability where the dye is to be applied di rectly to the fiber from an aqueous suspension. The general methods by which the dye compounds may be applied to the coloration of other materials are well known in the art and need not be described here.

In employing the anthraquinone compounds of our invention as dyes, they will ordinarily be applied to the material in the form of an aque ous suspension which can be prepared by grinding the dye to a paste in the presence of a sulfonated oil, soap or other suitable dispersing agent and dispersing the resulting paste in water. Dyeing operations can, withadvantage, be conducted at a temperature of 80-85 C., but any suitable temperaturemay be used. In accordance with the usual dyeing practice, the material to be dyed will ordinarily be added tothe aqueous dye bath at a temperature lower than that at which the main portion of the dyeing is to be effected, a temperature approximating 45-55" C., for example, following which the temperature of the dyebath will be raised to that selected for carrying out the dyeing operation. The temperature at which the dyeing is con- 'ducted will vary somewhat, depending, for example, on the particular material or materials undergoing coloration.

The amount of dispersing agent employed may be varied over wide limits. Amounts approximating to 200% by weight on the dye may be employed, for example. These amounts are not to be taken aslimits as greater or lesser amounts can be used. To illustrate, if the dye is ground to a sufllciently fine powder, dyeing can be satisfactorily carried out without the aid of a dispersing agent. Generally speaking, however, the use of a dispersing agent is desirable;

It willbe understood that the anthraquinone compounds of our invention may be applied to the material to becolored in any suitable manner. Coloration may be effected, for example, by dyeing, printing, or stenciling. Dispersing or solubilizing agents that can be employed for preparing suspensions of the dye include soap, sulphoricinoleic acid, salts of sulphoricinoleic acid, a water soluble salt of cellulose phthalate, cellulose succinate or cellulose mono-acetate diphthalate, for example, the sodium, potassium or ammonium salts, and sulfonated oleic, stearic or palmitic acid, or salts thereof, such, for ex-,

ample, as the sodium or ammonium salts.

The following examples illustrate how dyeing may be carried out in accordance with our in-' vention. Quantities are expressed in parts by weight.

Example A 2parts of me -ens H' K T o Ii-UHF In a i we. H

are finely ground with a dispersing agent such as soap or oleyl glyceryl sulfate and the resulting paste is dispersed in 1000 parts of water.

The dispersion thus prepared is heated to a temperature approximating 45-55? C. and. 100

parts of cellulose acetate silk, in the form of yarn or fabric, for example, are added to the dyebathafter which the temperature is gradually raised to -85 C. and the silk worked for several hours at this latter temperature." Sodium chloride may be addedas desired during the dyeing operation to promote exhaustion of the dyebath. Upon completion or the dyeing operation, the cellulose acetate silk is'removed, washed with soap, rinsed and dried. The cellulose acetate silk is colored a blue shade of good iastness to light. Example 8 2 parts of n Iii-CH:

HC--CH are finely ground with-a dispersingagentsuch as soap or oleyl glyceryl sulfate and the result-- ing paste is dispersed in 1000 parts of water. The dispersion thus prepared is heated to a temperature approximating 45-55 C. and parts 01' cellulose acetate silk, in the form 01' yarn or fabric, for example, are added to the dyebath after which the temperature is gradually raised to 80-85 C. and the silk worked for several 3 hours at. this latter temperature. Sodium chlo-. ride may be added as desired during the dyeing operation to promote exhaustion of the dyebath.

upon completion of the dyeing operatiomthe.

cellulose acetate silk is removed, washed with soap, rinsed and dried. The, cellulose acetate.

silk is colored a blue shade of good fastness to light.

While our invention has been illustrated in connection with the dyeing of cellulose acetate silk, it will be understood that dyeing operations can be carried out in a manner similar to that described above by the substitution of another organic derivative of cellulose material for cellulose acetate silk or by employing dye compounds other than those employed in the examples, or by substitution of both the material being dyed and the dye compounds ,of the examples.

We claim: v

1. As new products 'anthraquinone compounds characterized in that-they position the radical:

-- no -on H I! I g N( l)r- B wherein B represents amember selectedfroni the group consisting 01' hydrogen, -'(CH:)=OH and -(CH:):NH:, wherein a: is 1, 2, 3 or 4 and n is 1, 2, 3 or 4.

- 2. As new productsanthraquinone compounds w erein B represents a member selectedffrom' I the group consisting of hydrogen; --(CH:)=OH

- and -(CHi)-=NH:, wherein: is 1,. 2, 3'or 4 and.

nis1,2,3or4. V

3. A; new products anthraquinone' compounds having the general formulae: u

.nc,on H i i (0Ha).- 38 H|Q:- --CHi o n 'l i 0 N- oa, -n'

wherein 3 represents a from contain mm alpha the group consisting of hydrogen, (CH:)OH Y "and -(CH:)=NH:, wherein a: is- 1, 2', 3 or! and 4. As new products anthraquinon'e' compounds characterized in that they contain in an alpha position the ruri'urylamineradical.

5. As new products anthraquinone' compounds [characterized in thatuthey the tetrahydrofuri'urylamine radical. 6. The anthraquinone compound having the contain in an alpha formula:

I K m mc--o1n 7. The processor coloring which comprises applying thereto a nuclear-nonsulionated anthraquinone dye compound selected from the group ofv anthraquinone compounds v material made ofor containing an organic derivative ofcellulose characterized in that they contain in an alpha i wherein B represents a member selected from position a radical selected from: the group consisting of: n r HQ H .no-on H n 7 n" -N'(cm). LB and -N- cn. -s

the group consisting of hydrogen, -(CH:)OH

and -(CH:)=NH:, wherein z is 1, 2, 3 or- 4' and n is 1, 2, 3 or 4.

8. The process of coloring a material made of or containing an organic derivative 01' cellulose which comprises applying thereto a nuclear non-sulfonated anthraquinone dye compound selected from the group of anthraqulnone compounds characterized in that they contain in an alpha position a member selected from the group consisting of the furfurylamine radical and the tetrahydrofuriurylamine radical.

9. The process of coloring a material made of or containing an organic acid ester of cellulose which comprises applying thereto a nuclear nonsulionated anthraquinone dye compound selected from the group of anthraquinone compounds characterized in that they contain in an alpha position a radical selected from the group consisting of:

a HsC---CH:

nc---cn n a a wherein B represents a member selected from the group consisting of hydrogen, -(CH:)=OH and (CH:)=NH:. wherein a: is n is 1, 2, 3 or 4.

1, '2, 3 or 4 and 11. The process of coloring a cellulose acetate which comprises applying thereto a nuclear nonsulfonated anthraquinone dye compound selected from the group of anthraquinone compounds characterized in that they contain in an alpha position a member selected from the group con sisting of the furfurylamine radical and the tetrahydrofuriurylamine radical.

12. The process of preparing anthraquinone compounds which comprises condensing an anthraquinone compound containing an alpha negative substituent capable of being replaced by an amino group bythe action of an amine with an amine selected from the group consisting of H4C--CH| HC---0H H\ /H L1; andH;N--(CH;). B 0 0 wherein B represents a member selected from the group consisting of hydrogen, -(CH2)OH and -(CH2)=NI-Ia, wherein a: is l, 2, 3 or 4 and n is 1, 2, 3 or 4.

13. As new products, anthraquinone compounds characterized in that they contain in an alpha position a radical selected from the group consisting of:

wherein B represents a member selected from the group consisting of hydrogen, --(Cm)OH 1-iuriurylamino-4- JAMES G. McNALLY. JOSEPH mom. 

